WO2012038887A2 - Lithium accumulator - Google Patents

Lithium accumulator Download PDF

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Publication number
WO2012038887A2
WO2012038887A2 PCT/IB2011/054109 IB2011054109W WO2012038887A2 WO 2012038887 A2 WO2012038887 A2 WO 2012038887A2 IB 2011054109 W IB2011054109 W IB 2011054109W WO 2012038887 A2 WO2012038887 A2 WO 2012038887A2
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WO
WIPO (PCT)
Prior art keywords
accumulator
frames
electrolyte
lithium accumulator
electrodes
Prior art date
Application number
PCT/IB2011/054109
Other languages
English (en)
French (fr)
Other versions
WO2012038887A3 (en
Inventor
Prochazka (Jr.), Jan
Priochazka (Sr.), Jan
Jaroslav Polivka
Jiri Postler
Original Assignee
He3Da S.R.O.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority to CA2811875A priority Critical patent/CA2811875C/en
Priority to US13/823,889 priority patent/US9203123B2/en
Priority to PL11779486T priority patent/PL2619836T3/pl
Priority to MX2013002806A priority patent/MX341244B/es
Priority to AU2011306433A priority patent/AU2011306433B2/en
Priority to ES11779486.7T priority patent/ES2547779T3/es
Priority to JP2013529742A priority patent/JP5866107B2/ja
Priority to SI201130638T priority patent/SI2619836T1/sl
Priority to CN201180045880.9A priority patent/CN103140979B/zh
Priority to EP11779486.7A priority patent/EP2619836B1/en
Priority to BR112013006171-5A priority patent/BR112013006171B1/pt
Priority to RS20150624A priority patent/RS54243B1/en
Application filed by He3Da S.R.O. filed Critical He3Da S.R.O.
Priority to RU2013117740/07A priority patent/RU2577325C2/ru
Priority to DK11779486.7T priority patent/DK2619836T3/en
Priority to HRP20151047TT priority patent/HRP20151047T1/hr
Priority to KR1020137006462A priority patent/KR101887713B1/ko
Publication of WO2012038887A2 publication Critical patent/WO2012038887A2/en
Publication of WO2012038887A3 publication Critical patent/WO2012038887A3/en
Priority to ZA2013/01732A priority patent/ZA201301732B/en

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/50—Current conducting connections for cells or batteries
    • H01M50/572—Means for preventing undesired use or discharge
    • H01M50/584—Means for preventing undesired use or discharge for preventing incorrect connections inside or outside the batteries
    • H01M50/59—Means for preventing undesired use or discharge for preventing incorrect connections inside or outside the batteries characterised by the protection means
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • H01M10/0585—Construction or manufacture of accumulators having only flat construction elements, i.e. flat positive electrodes, flat negative electrodes and flat separators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/60—Heating or cooling; Temperature control
    • H01M10/65—Means for temperature control structurally associated with the cells
    • H01M10/655—Solid structures for heat exchange or heat conduction
    • H01M10/6556—Solid parts with flow channel passages or pipes for heat exchange
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/60—Heating or cooling; Temperature control
    • H01M10/65—Means for temperature control structurally associated with the cells
    • H01M10/656—Means for temperature control structurally associated with the cells characterised by the type of heat-exchange fluid
    • H01M10/6567—Liquids
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/70—Arrangements for stirring or circulating the electrolyte
    • H01M50/77—Arrangements for stirring or circulating the electrolyte with external circulating path
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/02—Details
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/04—Construction or manufacture in general
    • H01M10/0413—Large-sized flat cells or batteries for motive or stationary systems with plate-like electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/04—Construction or manufacture in general
    • H01M10/0486—Frames for plates or membranes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4242—Regeneration of electrolyte or reactants
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/60—Heating or cooling; Temperature control
    • H01M10/61—Types of temperature control
    • H01M10/613—Cooling or keeping cold
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/60—Heating or cooling; Temperature control
    • H01M10/64—Heating or cooling; Temperature control characterised by the shape of the cells
    • H01M10/647—Prismatic or flat cells, e.g. pouch cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/60—Heating or cooling; Temperature control
    • H01M10/65—Means for temperature control structurally associated with the cells
    • H01M10/654—Means for temperature control structurally associated with the cells located inside the innermost case of the cells, e.g. mandrels, electrodes or electrolytes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/60—Heating or cooling; Temperature control
    • H01M10/65—Means for temperature control structurally associated with the cells
    • H01M10/655—Solid structures for heat exchange or heat conduction
    • H01M10/6554—Rods or plates
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/60—Heating or cooling; Temperature control
    • H01M10/65—Means for temperature control structurally associated with the cells
    • H01M10/655—Solid structures for heat exchange or heat conduction
    • H01M10/6556—Solid parts with flow channel passages or pipes for heat exchange
    • H01M10/6557—Solid parts with flow channel passages or pipes for heat exchange arranged between the cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/60—Heating or cooling; Temperature control
    • H01M10/65—Means for temperature control structurally associated with the cells
    • H01M10/656—Means for temperature control structurally associated with the cells characterised by the type of heat-exchange fluid
    • H01M10/6567—Liquids
    • H01M10/6568—Liquids characterised by flow circuits, e.g. loops, located externally to the cells or cell casings
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/60—Heating or cooling; Temperature control
    • H01M10/66—Heat-exchange relationships between the cells and other systems, e.g. central heating systems or fuel cells
    • H01M10/663—Heat-exchange relationships between the cells and other systems, e.g. central heating systems or fuel cells the system being an air-conditioner or an engine
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the invention relates to a lithium accumulator comprising positive and negative electrodes with a minimum thickness of 0.5 mm, separated by separators, where each electrode is placed into holes in a frame, which is a part of set of frames arranged in a stack between marginal covers, with electrical insulation between the frames of electrodes with opposite polarity and additional current collectors between the frames of the same polarity.
  • Using high-capacity accumulators and accumulator modules is associated with a problem of ratio between the increasing accumulator power and weight vs. room available for removal of heat generated in chemical reactions during the accumulator charging and discharging. Any major overheating of the accumulator can result in a fire or explosion. Operation of the accumulator outside the safe temperature range can also significantly reduce the accumulator service life. Maintaining the operating temperature in a safe range to eliminate the above-described accidents requires additional equipment to ensure greater exchange of heat. Such equipment may also be required where extremely low temperatures reduce the accumulator power substantially and it is necessary to raise the operating temperature by heat exchange.
  • the accumulator cooling is provided by the current collectors on cells consisting of thin film planar lithium electrodes.
  • the collectors transfer the heat losses from the battery via an electro insulating, thermally conductive film to a heat exchange plate on the top of the accumulator, which can optionally be connected to a vehicle cooling system.
  • the heat is removed through the current collectors directly from inside of the accumulator.
  • the problem still is in further transfer of heat from such folio current collectors to the actual heat exchange system.
  • the heat transfer is reduced by using an electro insulating film and the heat transfer capacity is limited to a single heat exchange plate.
  • PCT application WO WO2010031363 discloses a lithium accumulator comprising metal frames arranged in a stack, where each frame contains a puncture, in which one thick three dimensional (3D) electrode is placed, and whereby the electrodes of opposite polarity are separated by separators and the frames with electrodes of opposite polarity are isolated from each other.
  • the metal frames allow better heat transfer from the inside of the accumulator stack, they do not guarantee a reliable heat transfer from large-sized electrodes and especially from modules with number of stacks arranged side by side. I
  • a lithium accumulator comprising positive and negative electrodes separated by separators, deposited into holes in frame, which is a part of a set of frames arranged in a stack between marginal covers, with electrical insulation between the frames of electrodes opposite polarity and additional current collectors between frames of electrodes with identical polarity, whereby each frame comprises at least one channel for passage of a heat exchange medium and the channels in the individual frames are interconnected.
  • Each frame contains more than one identically situated hole for an electrode and at least one channel identically positioned between the hole openings, whereby the electrodes placed into the holes in the frames form together with the adjacent frame walls, separators, electro-insulating materials and current collectors the individual accumulator modules and the channels create passages for the heat exchange medium.
  • the covers include a system of interconnected grooves on the inner side, wherein at least one cover is connected to the electrolyte inlet.
  • a distribution board with holes connecting the groove system with the openings in the frame is positioned between the cover and the first adjacent frame. Pipes ending in the holes at the distribution board are located within the passages and connected to the heat exchange media distribution system. Expanded metal or a grid can be used instead of the distribution board in some cases.
  • the heat exchange medium distribution system can include a pump and an external heat exchanger.
  • the heat exchange medium is an electrolyte and the frames carrying identical electrodes are provided with grooves on their adjacent side connecting the passages with the electrode holes.
  • one cover comprises an inlet of electrolyte and the other cover is provided with an inlet branch for connecting to an air-relief valve.
  • the electrolyte external cooling system is used, one cover is connected to the inlet piping of the electrolyte distribution system and the other cover is connected to the return piping of the electrolyte distribution system.
  • the electrolyte distribution system includes a pump and an external heat exchanger, where an electrolyte regeneration unit may also be incorporated into the return piping.
  • the frames have external electrical contacts and electrically conductive foils as additional current collectors between the frames of electrodes with the same polarity.
  • Said additional collectors can be perforated, whereby the electrically interconnected frames with identical polarity form the accumulator poles.
  • the electro insulating material is a plasma coated porous electro insulating material.
  • This material can be selected from the group of ceramic oxides Al 2 O 3 , SiO 2 , ZrO 2 polytetrafluoroethylene, polyfluoride-hexafluoropropene, polycycloolefine.
  • Both covers are preferably connected to one pole of the accumulator.
  • the invention is based on the use of a stack of metal frames with holes into which the 3D electrodes are placed. It is to be understood that the term 3D refers to the electrodes having a minimum thickness of 0.5 mm contrary to thin film electrodes having substantially lower thickness. Placing the electrodes into frames provides the accumulator necessary mechanical resistance against impact, pressure and vibrations. Moreover, the frames allow distribution and exchange of heat inside the accumulator and also serve as current collectors, poles of the individual electrodes and the current terminals.
  • the external heat exchange medium is supplied into the accumulator by means of tubes passing through the passageways formed by channels in the frames and usually connected to an external heat exchange medium circulation system.
  • the electrolyte is supplied to the electrodes by mean of mutually connected passages and grooves in the frames.
  • the electrolyte media is of the same type as present in the electrodes, separators and the distribution system.
  • the entire accumulator stack can be situated in a casing and connected to an external heat exchange media (electrolyte) distribution system.
  • marginal covers with grooves, distribution boards with holes, and frames with distribution grooves or porous ceramic or metal layer render additional means ensuring perfect filling up of the accumulator by the electrolyte as well as the replacement and degassing thereof.
  • Integration of an electrolyte regeneration unit and a cleaning filter further enhance the service time of the electrolyte and consequently increase the life of electrodes and accumulator as a whole.
  • the compact configuration of such effectively cooled modules enables to construct an accumulator with an optimal distribution of its volume between the frames, cooling system and electrode capacity, achieving the specific capacity of at least 250 Wh/liter, when using conventional active materials for electrodes, such as NMC (LiCo 1/3 Mn 1/3 Ni 1/3 O 2 ) and graphite.
  • Fig. 1 is a front sectional view of an accumulator with a separated external circulation distribution system for a heat exchange medium
  • Fig. 2 is a front sectional view of a frame with holes for electrodes and channels for heat exchange media;
  • Fig. 3 is a plan view of an electrolyte distribution board
  • Fig. 4 is a bottom view of the upper marginal cover with grooves for distribution of electrolyte and passages for the heat exchange media;
  • Fig. 5 is a partial sectional view of the internal part of the accumulator - one module with its components shown in detail;
  • Fig. 6 is a front sectional view of an accumulator with a circulation distribution system of electrolyte as a heat exchange media and with the direct flow of electrolyte through the accumulator;
  • Fig. 7 is an internal view of the upper and lower cover with grooves for electrolyte distribution according to Fig. 6;
  • Fig 8 is a front sectional view of an accumulator with the circulation distributing system of electrolyte as a heat exchange media and with the return flow of electrolyte;
  • Fig. 9a is a view of a frame with grooves for distribution of electrolyte to electrodes
  • Fig. 9b is a view of a frame with grooves for distribution of electrolyte to electrodes and outside the frame;
  • Fig. 9c is a view of a frame with grooves for distribution of electrolyte to electrodes and the distribution system;
  • Fig. 10 is a front sectional view of a simple accumulator without casing.
  • FIG. 1 A front sectional view of an accumulator with an external circulation system of the heat exchange media is shown in Fig. 1.
  • Individual metal frames 3 are stacked one above the other in a housing 10 between an upper cover 1a illustrated in a plan view in Fig. 4, and a lower cover 1b. The same frames are shown in a plan view in Fig. 2.
  • Each frame contains a set of three identically positioned holes for electrodes 31 and a set of identically displayed channels 32. All holes 31 of each frame 3 are filled up with either 3D hard-pressed positive electrodes 4a or 3D hard-pressed negative electrodes 4b, as shown in detail together with other components in Fig 5.
  • the term 3D shall mean the so-called three-dimensional electrodes and according to this invention, electrodes having a minimum thickness of 0.5 mm.
  • the number of holes 31 for the electrodes and channels 32 in one frame 3 is practically unlimited and depends on desired accumulator capacity.
  • All electrodes 4a in the holes 31 of the frame 3 constitute together one electrode of one polarity; in this embodiment a positive electrode. All electrodes 4b in the next frame 3 constitute together one electrode of the other polarity, in this embodiment a negative electrode 4b.
  • Each pair of frames 3 with electrodes 4a and 4b are separated by separators 5 and constitute one set of frames 3 representing one accumulator cell.
  • the openings 31 and accordingly the electrodes 4a, 4b, can have any flat shape, including the illustrated circular profile, with respect to the manufacturing technology.
  • the system of channels 32 identically positioned above each other form together passages 34 for distribution of a heat exchange media.
  • the frames 3 with the hard-pressed electrodes 4a, 4b conduct away and distribute the heat losses generated during chemical reactions accompanying the accumulator charging and discharging. Alternatively, the frames bring in and distribute heat supplied from an external source via heat transfer medium to increase the temperature of the accumulator.
  • Fig1 shows the pipes for heat exchange media 14 installed into passages 34 .
  • each electrode 4a, 4b after being hard-pressed into the hole 31, has a thickness of 2 mm.
  • the frames 3 are of the same thickness as the electrodes 4a, 4b.
  • An electro-insulating material 55 is inserted between the frames with different polarity. Suitable electro-insulating materials are chemically and thermally resistant substances, for example ceramic oxides, such as Al 2 O 3 , SiO 2 , ZrO 2 .
  • Another electro-insulating materials can be polytetrafluoroethylene PTFE (Teflon), a polymeric fluoroelastomer such as vinylidene fluoride-hexafluorporopene, also known under the trademark Viton or cycloolefine polymer known under the brand Zeonor.
  • Teflon polytetrafluoroethylene PTFE
  • Viton vinylidene fluoride-hexafluorporopene
  • cycloolefine polymer known under the brand Zeonor.
  • Additional current collectors electrically conductive foils 51, 53, in the form of grids, expanded metal or foils made of a conductive metal are inserted between the frames 3 between electrodes of the same polarity.
  • the electrically conductive foils 51 and 53 are perforated 56 in the area facing the electrodes to facilitate the passage of electrolyte.
  • These additional current collectors enable the electrical charge transfer to the frames 3 as the main current collectors.
  • the frames 3 with electrodes of the same polarity are further provided with contacts 57, 58, which, in this embodiment, are connected to the positive pole 52 of the accumulator on one side and to the negative pole 54 of the accumulator on the other side. Possible material compositions and different variants of 3D electrode configurations are described in more details in WO2010031363.
  • the individual heat transfer tubes 14 are inserted into passages 34.
  • the modules 20 are completed by an upper distribution board 2a and a lower distribution plate 2b. Both plates shown in the plan view of Fig. 3 have a system of punctures 21 above the surfaces of electrodes 4a, 4b and are practically identical.
  • the punctures 21 enable the individual modules 20 supply and draining off the electrolyte during its replacement, and also degassing of the internal space of the modules.
  • the upper cover 1a and the lower cover 1b are fitted to the distribution boards 2a, 2b, on the inner side with a system of distribution grooves 11, as shown in the plan view of the cover 1a in Fig. 4.
  • the marginal openings 17 on the covers 1a, 1b are designed for safe connection of covers 1a, 1b, and fixation of the stack of frames 3 between them by means of bolts, not shown in the drawings.
  • the electrolyte is supplied into the upper cover 1a through an inlet 12, while the lower cover 1b can be similarly equipped with an electrolyte outlet, not shown in this Figure.
  • the heat exchange pipes 14 are fastened to and sealed into an upper divider 13a.
  • the divider 13a is located above the cover 1a and defines an upper chamber 15a.
  • the heat transfer tubes 14 are fastened to and sealed in a bottom divider 13b situated under the cover 1b and defining a lower chamber 15b.
  • the upper chamber 15a is connected through an inlet piping 81 to a pump 8, which pumps the heat exchange medium from a heat exchanger 18 to the interior of the accumulator housing 10.
  • the lower chamber 15b is connected to the return piping 82 with a heat exchanger 18.
  • the tubes 14 above the covers 1a, 1b be individually connected directly to the intake manifold 81 and to the return piping 82.
  • a car radiator can be used as a heat exchanger. It is obvious for those skilled in art that the above described cooling system can be applied also in the case where the accumulator is composed of only one module 20 with one passage 34.
  • Fig. 6 shows another variant of the accumulator cooling, in which an electrolyte is used as a heat transfer medium directly flowing through the accumulator.
  • a suitable liquid electrolyte for temperatures up to 85°C is for example LiPF 6 in a solution of ethylene carbonate (EC) and propylene carbonate (PC), etc.
  • the manifold 81 connected to the pump 8 enters directly into the center of the upper cover 1c as shown in the plane view of Fig. 7.
  • the upper cover 1c is practically identical as the lower cover 1d, with the manifold connected to the return piping 82 in the centre of the cover.
  • the distributions boards 2a, 2b are inserted between the covers 1c, 1d and the modules 20 to enable supply of an electrolyte distributed through grooves 11 into the individual modules 20 and similar to the previous version, the frames 3 include the system of holes 31 for electrodes and system of channels 22 constituting passages 34 for distribution of the heat exchange media, in this case an electrolyte.
  • the frames 3 can be provided with a system of grooves 36, 37, 38 on one or both contact surfaces.
  • the system of grooves is limited to internal grooves 36, which distribute the electrolyte to openings 32 with electrodes 4a 4b.
  • this system may be extended to include outer grooves 37 that allow the electrolyte to be also supplied from the lateral compartment 35 of the housing 10.
  • Fig. 9c shows a system of grooves 38 made in the frame 3 of the accumulator with an electrolyte as heat exchange media.
  • the grooves 38 connect the passages 34 directly with holes 31.
  • the electro-insulating material 55 can be replaced with a plasma-coated porous electrical insulating layer across the whole connecting surfaces of the frame 3, which also allows penetration of the electrolyte from passages 34 and lateral space 35 to electrodes 4a, 4b and the separators 5.
  • a regeneration unit 19 is incorporated into the return piping 82 upstream of the heat exchanger.
  • Such unit can be a filter for electrolyte cleaning from undesired products of chemical reactions, which take place in the accumulator modules 20.
  • Such products may be HF, H 2 O, or released ions of manganese and its compounds, mechanical particles, etc.
  • the regeneration unit 19 can work on mechanical, chemical, sorption and electrochemical principle, using lithium membranes, etc. Electrolyte cleaning significantly prolongs the accumulator operation life.
  • Fig. 8 shows another embodiment of an electrolyte-cooled accumulator, which differs from the previous versions only by the way in which the electrolyte flows through the accumulator.
  • the return piping 82 is connected to the housing 10 in the area of the upper cover 1c so the electrolyte, after flowing through the passages 34, returns from the bottom part of the housing space 10 across the lateral compartment 35 to the top part of the housing 10. Then, the electrolyte is delivered through the piping 82 to the regeneration unit 19.
  • the housing 10 can be provided with cooling fins on any suitable surface.
  • Fig. 10 shows a simple version of the accumulator where the accumulator does not have an external heat exchange media distribution system, electrolyte container and housing.
  • the housing of the accumulator is defined only by outer surfaces of the frames 3 and the covers 1c, 1d.
  • the accumulator is cooled by natural circulation of the heat exchange medium, along the large area of metal frames 3.
  • the removal of heat from the inside of the accumulator is happening through the circulation of electrolyte between electrodes 4a. 4b in openings 31, passages 34 and covers 1c, 1d due to the differences between temperatures in various parts of the accumulator 31.
  • the cover 1d is connected to the inlet 12 for electrolyte fill up and the cover 1c is provided with inlet branch 16 for connection to a gas release valve (not shown).
  • the covers 1c, 1d can also be provided with cooling fins.
  • This simplified version is suitable for accumulators of lower power, producing smaller heat losses, for example starter accumulators.
  • the invention can be used for construction of high-capacity energy storage accumulators and accumulators with high safety for use in vehicles exposed to extreme thermal conditions, shocks and vibrations.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Secondary Cells (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
  • Battery Mounting, Suspending (AREA)
  • Connection Of Batteries Or Terminals (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Supply Devices, Intensifiers, Converters, And Telemotors (AREA)
PCT/IB2011/054109 2010-09-23 2011-09-20 Lithium accumulator WO2012038887A2 (en)

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US13/823,889 US9203123B2 (en) 2010-09-23 2011-09-20 Lithium accumulator
PL11779486T PL2619836T3 (pl) 2010-09-23 2011-09-20 Akumulator litowy
MX2013002806A MX341244B (es) 2010-09-23 2011-09-20 Acumulador de litio.
AU2011306433A AU2011306433B2 (en) 2010-09-23 2011-09-20 Lithium accumulator
ES11779486.7T ES2547779T3 (es) 2010-09-23 2011-09-20 Acumulador de litio
JP2013529742A JP5866107B2 (ja) 2010-09-23 2011-09-20 リチウム蓄電池
SI201130638T SI2619836T1 (sl) 2010-09-23 2011-09-20 Litijev akumulator
EP11779486.7A EP2619836B1 (en) 2010-09-23 2011-09-20 Lithium accumulator
CN201180045880.9A CN103140979B (zh) 2010-09-23 2011-09-20 锂蓄电池
CA2811875A CA2811875C (en) 2010-09-23 2011-09-20 Lithium accumulator
RS20150624A RS54243B1 (en) 2010-09-23 2011-09-20 LITHIUM BATTERY
BR112013006171-5A BR112013006171B1 (pt) 2010-09-23 2011-09-20 Acumulador de lítio
RU2013117740/07A RU2577325C2 (ru) 2010-09-23 2011-09-20 Литиевый аккумулятор
DK11779486.7T DK2619836T3 (en) 2010-09-23 2011-09-20 Litiumakkumulator
HRP20151047TT HRP20151047T1 (hr) 2010-09-23 2011-09-20 Litijev akumulator
KR1020137006462A KR101887713B1 (ko) 2010-09-23 2011-09-20 리튬 축전지
ZA2013/01732A ZA201301732B (en) 2010-09-23 2013-03-07 Lithium accumulator

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CZPV2010-703 2010-09-23
CZ20100703A CZ2010703A3 (cs) 2010-09-23 2010-09-23 Lithiový akumulátor

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US20130177786A1 (en) 2013-07-11
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RS54243B1 (en) 2015-12-31
CZ2010703A3 (cs) 2012-04-04
RU2013117740A (ru) 2014-10-27
DK2619836T3 (en) 2015-11-02
EP2619836A2 (en) 2013-07-31
CL2013000804A1 (es) 2014-03-07
KR101887713B1 (ko) 2018-09-10
KR20140027900A (ko) 2014-03-07
HRP20151047T1 (hr) 2015-11-06
CA2811875C (en) 2018-01-02
JP2013541157A (ja) 2013-11-07
PL2619836T3 (pl) 2016-02-29
JP5866107B2 (ja) 2016-02-17
WO2012038887A3 (en) 2012-06-07
CY1116696T1 (el) 2017-03-15
MX2013002806A (es) 2013-04-09
ES2547779T3 (es) 2015-10-08
BR112013006171B1 (pt) 2020-02-27
BR112013006171A2 (pt) 2016-06-07
EP2619836B1 (en) 2015-08-05
RU2577325C2 (ru) 2016-03-20
AU2011306433B2 (en) 2016-03-10
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HUE027984T2 (en) 2016-11-28
ZA201301732B (en) 2013-11-27
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PT2619836E (pt) 2015-10-09
SI2619836T1 (sl) 2015-11-30
CN103140979A (zh) 2013-06-05

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